Treatment of rubber



Patented May 2, 1933 PATENT Free WILLIAM I. TEE HORST, OF PAOKANAG'K LAKE, NEW JERSEY, ASSIGNOR TO THE NAUGATUGK CHEMICAL COMPANY, OF NAUGATUCK, CONNECTICUT, A CORPORATION OF CONNECTICUT TREATMENT OF RUBBER No Drawing. Original application filed December 4, 1929, Serial No. 411,666. Divided and this application filed July 28, 1931.

This invention relates to the treatment of rubber and similar materials, more particularly to a treatment of the same with the rearranged reaction products of ketones and 5 amino compounds, or certain derivatives of the foregoing. It also relates to the products of such treatment.

An object of this invention is to provide materials having the property of retarding the deterioration of rubber. A still further object is to provide materials having yulcanization-accelerating properties. Other objects will be apparent from the herein set forth description.

Accordingly the invention comprises treat-- ing rubber or similar materials with a rearranged reaction product of a lretone and an aromatic amino compound. Such materials are stable, and will when usedin rubber exhibit at least one of the above mentioned properties. I 3

Examples of rearranged reaction products of ketones-acetone-diphenyl guanidine rearranged in the presence of aniline hydro- 5 chloride, acetone-alpha-napht-hyl amine rearranged in the presence of aniline hydrochloride. 1

Instead of the ketones mentioned above the following may be used: phorone, diethyl ketone, benzo phenone, aceto-phenone, di-

chloracetone, aldol acetone, allyl-acetone,

benzal acetone, diacetyl, acetyl-acetone, acetonyl-acetone, salicyl aldehyde-acetone, furfural-acetone, mesityl oxide, diacetone'alcohol.

Instead of the aromatic amino compounds mentioned above there may be used: monochloro aniline, ortho-toluidine, meta toluidine, para-toluidine, xylidincs, alpha-naph- 40 thylamine beta naphthylamine, amino diphenyl, dinaphthylamines, asymmetric diphenyl hydrazine, diamino diphenyl sulphide, diamino diphenyl polysulphides, diamino dinaphthyl sulfides, p-amino benzylaniline, dinaphthyl diamino ethane, ditolyl Serial No. 553,642.

diamino ethane, p-amino-p'naphthylamino diphenyl methane. p-p-diamino diphenyl dimethyl methane, p-p-dinaphthyl amino diphenyl dimethyl methane, phenyl beta naphthyl guanidine, phenyl-o-tolyl guanidine, dio-tolyl biguanide, monophenyl biguanide, diphenyl biguanide, diphenyl acetamidine, ophenylene diamine. m-phenylene diamine, p -phenylene diamine, dimethyl p-phenylene chamine, m-toluylene diamine, benzidine, naphthylene diamine; 2,2-diamino diphenyl; 2,t-diamino diphenyl; diphenyLp-phenlyene diamine, ditolyl-p-phenylene diamine, dinaphthyl-p-phenylene diamine, diphenylbenzidine. dinaphthyl-benzidine, naphthylm-toluylene, diamine, dinaphthyl-m-toluylene diamine; 2,4-diamino-diphenylamine; 4, l-diamino diphenylamine; or mixtures of any of the foregoing aromatic amino compounds with a phenol such as phenol, alphanaghthol betanaphthol.

In the reactions of ketones with salts of aromatic amino compounds, such aromatic amino compounds as contain at least one ortho or para carbon atom linked to hydrogen. have been found to be most suitable.

Example 1Rearranged reaction products of ketones and amino compounds. 105 parts of acetone-aniline reaction product, prepared by reacting under heat and pressure aniline and acetone in the presence of a dehydrating agent such .as iodine as described in by copending application Serial No. 411,- 665, filed December l, 1929 were mixed with 100 grams of aniline and 20 cc. of concentrated acqueous hydrochloric acid. The mixture was kept at a temperature of 90 C. during 30 hours. At the end of 30 hours the hydrochloric acid was neutralized with caustic soda and unreacted aniline was removed by vacuum distillation. The residue weighed 1.20 grams and became brittle on cooling. It can be ground to a light brown powder. The product was tested by incorporating 1.5 parts in a tire tread compound containing 100 parts of rubber, parts carbon black and a mixture of 1 part of bexamethylene tetramine and .25 parts of diphenyl guanidine, and vulcanizing and ageing. The tensile strengths before and after ageing are shown below.

The accelerating properties of the reaction product is shown by incorporating 1.5 parts of the reaction product in a tire tread compound similar to that above but from which the usual accelerator was omitted.

Cure Tensiles Blank 90 at 45# 1830 4- reaction product 90 at 45# 3 595 The accelerating properties are also shown by incorporating 1 part of the reaction product in a rubber mix consisting of 100 parts of rubber, 10 parts of zinc oxide, and 3 parts of sulphur.

Cure Tensiles Blank-no accelerator at 40;? 402 reaction product 60 at 40%! 2245 The simplest acetone aniline reaction product, on rearranging in the presence of aniline hydrochloride, would yield a product of the probable formula v oGHlNHz I which can be called p, p-diamino-di-phenyldi-methyl methane. The reaction product of one mole of mesityl oxide and one, mole of aniline On rearranging would yield a compound of the probable formula:

And finally, a phorone-aniline reaction prod uct upon rearranging would yield a product of the probable formula CH3 7 CH3 oHrNHz It is obvious that the above and similar products correspond to the probable general formula NHa-Ar-C-AW-NHz.

' ence of aromatic amine salts generally but differing in chemical nature depending on whether or not the amine of the amine salt used to rearrange, is the same or different from the amine originally used to prepare the ketone-amine reaction product. For example instead of'using aniline hydrochloride as in the Example 1 above, the hydrochloride of naphthylamine or of diphenyl guanidine may be used. Also when the amine used in the preparation of the ketone-amine is" differentfrom the rearranging amines, rearranged ketone-amines of a mixed character result. For example the reaction product of acetone and alphaor beta-naphthylamine may be rearranged in the presence of aniline hydrochloride, and the reaction product of acetone and l, l-dia1nino-diphenyl amine may be rearranged in the presence of toluidine hydrochloride.

' .It is to be understood that a mixture of the reactionproducts'or derivatives may be used in rubber instead of a single reaction product or derivative. Also that a mixture of ketones, or a single ketone may be reacted With a single amino compound or with a mixture of amino compounds, such as described herein, to give products that may be used in rubber in the 'same manner.

The chemicals disclosed may be used to improve the properties as mentioned herein of inner'tubes, tires, thread, hosejdipped goods, mechanical goods, latex or articles madefrom latex etc.

Salt of an aromatic amino compound and amine salt in the claims are to be understood as meaning the acid addition product of the amines or amino compounds, such as the hydrochloride, the sulfate, the phosphate, the acetate, etc. Also the term rubher is to be construed as including natural rubber, gutta, percha, balata, synthetic rubber, or other rubber-like materials.

This case is a division of case Serial No.

411,666, filed Dec. 4., 1929.

With the detailed description given above, it will be obvious that modifications will suggest themselves without departing from a not desired to limit the invention otherwise than as set forth in the appended claims.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A method of treating rubber which comprises treating rubber with a reaction product of a ketone and an aromatic amine which product has been further reacted with a salt of a diiierent aromatic amine.

'2. A method of treating rubber which comprises treating rubber with a reaction product of an aliphatic ketone and an arcmatic amine rearranged in the presence of a salt of a different aromatic amine.

3. A method of treating rubber which comprises treating rubber with a reaction product of a ketone and an aromatic amine rearranged in the presence of a salt of a different aromatic amine.

4. A method of treating rubber which comprises treating rubber with a reaction product of a ketone and a primary aromatic amine rearranged in the presence of a salt of a different primary aromatic amine.

5. A method of treating rubber which comprises treating rubber with a compound having the probable general formula NHzA1'--OATNH2,

wherein Ar and A1 are different arylene groups, and R and R are aliphatic hydrocarbon groups which may be saturated or unsaturated.

6. A method of treating rubber which comprises treating rubber with a reaction product of acetone and a naphthylamine rearranged in the presence of a salt of a primary aromatic amine other than said naphthylamine.

7 A method of treating rubber which comprises treating rubber with a reaction product of acetone and naphthylamine rearranged in the presence of aniline hydrochloride.

8. A method of treating rubber which comprises treating rubber with a reaction product of acetone and a salt of a toluidine rearranged in the presence of a primary aromaticamine other than said toluidine.

9. A method of treating rubber which comprises treating rubber with a reaction product of acetone and a toluidine rearranged in the presence of aniline hydrochloride.

10. A method of improving the properties of rubber which comprises vulcanizing rubber in the presence of a reaction product of an aliphatic ketone and an aromatic amine rearranged in the presence of a salt of a different aromatic amino compound.

11. A method of improving the properties of rubber which comprises Vulcanizing rubber in the presence of a reaction product of a ketone and an aromatic amine rearranged in the presence of a salt of a diflerent aromatic amine.

12. A method of improving the properties of rubber which comprises vulcanizing rubber in the presence of a reaction product of a ketone and a primary aromatic amine rearranged in the presence of a salt of a different primary aromatic amine.

13. A method of improving the properties of rubber which comprises vulcanizing rubber in the presence of a reaction product of acetone and a naphthylamine rearranged in the presence of a salt or: a primary aromatic amine other than said naphthylamine.

14. A method of improving the properties of rubber which comprises vulcanizing rul her in the presence of a reaction product of acetone and naphthylamine rearranged in the presence of aniline hydrochloride.

15. A method of improving the properties of rubber which comprises vulcanizing rubber in. the presence or" a reaction product of acetone and a toluidine rearranged in the presence of a salt of a primary aromatic amine other than said toluidine.

16. A method of improving the properties of rubber which comprises vulcanizing rubher in the presence of a reaction product of acetone and a. toluidine rearranged in the presence of aniline hydrochloride.

17. A rubber product which has been treated with a reaction product of a ketone and an aromatic amine rearranged in the presence of a salt or" a different aromatic amine.

18. A rubber product which has been treated with a reaction product of a ketone and a primary aromatic amine rearranged in the presence of a salt of a different primary aromatic amine.

19. A vulcanized rubber product containing rubber which has been vulcanized in the presence of a reaction product of a lretone and an aromatic amine rearranged in the presence of a salt of a different aromatic amine.

20. A vulcanized rubber product containing rubber which has been vulcanized in the presence of a reaction product of a lretone and a primary aromatic amine rearranged in the presence of a salt of a different primary aromatic amine.

Signed at Montclair, county of Essex, State of New Jersey, this 24th day of July 1931.

WILLliAM P. TER HORST. 

